CN114103377A - High-barrier heat-sealable degradable film and preparation method thereof - Google Patents
High-barrier heat-sealable degradable film and preparation method thereof Download PDFInfo
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- CN114103377A CN114103377A CN202111529829.7A CN202111529829A CN114103377A CN 114103377 A CN114103377 A CN 114103377A CN 202111529829 A CN202111529829 A CN 202111529829A CN 114103377 A CN114103377 A CN 114103377A
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- JAUVCBJVIFFHEI-UHFFFAOYSA-N benzyl-methyl-dioctadecylazanium Chemical group CCCCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCCCC)CC1=CC=CC=C1 JAUVCBJVIFFHEI-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of packaging materials, in particular to a high-barrier heat-sealable degradable film and a preparation method thereof. The high-barrier heat-sealable degradable film comprises a substrate layer and a coating barrier layer positioned on the upper surface of the substrate layer; the coating barrier layer comprises polyvinyl alcohol emulsion, graphene, bonding resin, a curing agent, a coupling agent and a solvent. The high-barrier heat-sealing degradable film provided by the invention is strong in barrier property, good in heat-sealing property and completely biodegradable, and the product is suitable for the packaging fields of food, medicines, daily chemicals, medical instruments and the like. The invention also provides a preparation method of the high-barrier heat-sealable degradable film.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to a high-barrier heat-sealable degradable film and a preparation method thereof.
Background
The use of plastic packaging products brings great convenience to the life of people, and becomes an indispensable packaging material for human survival and social development, but the treatment of waste plastic packaging products causes people to have headache outside. Because of the non-degradability of the waste plastic products, the waste plastic products can only be burned or buried, but a large amount of harmful gas is generated in the burning process, the land filling occupies a large amount of land, the crop cultivation is influenced, and the occupied land can not be recovered for a long time, and the sustainable utilization of the land is influenced. With the increasing use amount of plastic packaging articles year by year, the problem of environmental pollution is more and more prominent. Therefore, achieving environmental friendliness and sustainable development of plastic packaging articles is one of the most attractive and challenging directions today.
Meanwhile, in order to meet the packaging requirements, for example, in order to make the packaging material have better barrier property and heat sealing property, the packaging material adopting a plurality of material structures is a common way at present, and although the combination way can meet the packaging requirements of different occasions, the combination way increases difficulty for subsequent recycling after the packaging mission is finished. With the implementation of the plastic limit order and the improvement of the environmental protection requirement, the material which is made of single material, is environment-friendly, can be recycled and reused and is degradable is concerned. Further, as people's consciousness about health and hygiene is increased, a packaging film applied to the field of food packaging and the like is required to have not only good barrier properties but also good heat sealability.
Therefore, how to obtain a high-barrier heat-sealable degradable film becomes a problem to be solved at present.
Disclosure of Invention
The invention provides a high-barrier heat-sealable degradable film.
The technical scheme adopted by the embodiment of the invention is as follows:
specifically, one embodiment of the invention provides a high-barrier heat-sealable degradable film, which comprises a substrate layer and a coating barrier layer positioned on the upper surface of the substrate layer;
the coating barrier layer comprises polyvinyl alcohol emulsion, graphene, bonding resin, a curing agent, a coupling agent and a solvent.
In some embodiments, the mass ratio of the polyvinyl alcohol emulsion to the graphene is (30-50): (0.1-10).
In other embodiments, the mass ratio of the polyvinyl alcohol emulsion to the graphene to the adhesive resin to the curing agent to the coupling agent to the solvent is (30-50): (0.1-10): (5-20): (0.1-5): (0.5-5): (10-64.3).
Alternatively, the bonding resin includes, but is not limited to, a resin prepared from butyl methacrylate, ethylene glycol dimethacrylate and urethane resin in parts by mass of 2: 1: 1 are mixed.
Alternatively, the curing agent includes, but is not limited to, a diethylmalonic acid blocked isocyanate.
Alternatively, the coupling agent includes, but is not limited to, gamma- (2, 3-glycidoxy) propyltrimethoxysilane; the solvent comprises but is not limited to water and isopropanol which are mixed according to the mass ratio of 3: 1.
In some embodiments, the substrate layer comprises at least three layers, namely an upper surface layer, a middle barrier layer and a heat sealing layer from top to bottom;
the intermediate barrier layer comprises a modified polylactic acid resin;
the modified polylactic resin comprises, by mass, 0.1-5 parts of a layered nano inorganic material, 0.1-8 parts of a coupling agent, 0.1-5 parts of a super dispersant, and 82-99.7 parts of polylactic resin.
Optionally, the layered nano inorganic material includes, but is not limited to, at least one of montmorillonite, layered silicate, mica powder, and kaolin.
The coupling agent used in the modified polylactic acid resin may be the same as or different from the coupling agent added in the coating barrier layer.
In some embodiments, the hyperdispersant includes, but is not limited to, lubol Solplus DP 310.
In some embodiments, the upper surface layer comprises, by mass, 1 to 5 parts of the functional masterbatch and 95 to 99 parts of the polylactic acid resin.
In some embodiments, the heat-sealing layer comprises, by mass, 1 to 10 parts of a compatibilizer, 1 to 5 parts of a functional master batch, 25 to 80 parts of polyethylene terephthalate-1, 4-cyclohexanedimethanol ester, and 5 to 73 parts of polylactic acid resin.
Optionally, the compatibilizer includes, but is not limited to, at least one of an ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, an ethylene-acrylate-maleic anhydride copolymer, an ethylene-vinyl acetate copolymer, a maleic anhydride grafted ethylene-octene copolymer, an ethylene-acrylic acid copolymer, and a glycidyl methacrylate grafted ethylene-octene copolymer.
Optionally, the functional master batch comprises, by mass, 0.5-5 parts of a lubricant, 1-10 parts of an opening agent, 0.5-5 parts of an antioxidant and 80-98 parts of polylactic resin.
Optionally, the lubricant includes, but is not limited to, one or both of erucamide and oleamide.
Optionally, the opening agent includes, but is not limited to, silicon dioxide.
Optionally, the antioxidant includes, but is not limited to, a 2: 1, and mixing to obtain the product.
In some embodiments, the total thickness of the high-barrier heat-sealable degradable film is 10-80 μm;
wherein the thickness of the coating barrier layer is 1-4 μm;
the thickness of the upper surface layer and the heat sealing layer is 1-3 mu m;
the thickness of the intermediate barrier layer is 7 to 70 μm.
An embodiment of the invention provides a preparation method of a high-barrier heat-sealable degradable film, which comprises the following steps:
obtaining a substrate layer;
disposing a coating barrier layer on an upper surface of the substrate layer; the coating barrier layer comprises polyvinyl alcohol emulsion, graphene, bonding resin, a curing agent, a coupling agent and a solvent.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts; in the following description, the drawings are illustrated in a schematic view, and the drawings are not intended to limit the present invention.
FIG. 1 is a schematic structural diagram of a high-barrier heat-sealable degradable film according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a film according to a comparative example of the present invention;
FIG. 3 is a schematic diagram of another embodiment of a film according to a comparative example of the present invention;
FIG. 4 is a schematic structural diagram of yet another film provided in a comparative example of the present invention;
FIG. 5 is a schematic structural view of yet another film provided in a comparative example according to the present invention;
FIG. 6 is a schematic structural diagram of yet another film provided in a comparative example of the present invention; .
Reference numerals:
10 substrate layer 11 and upper layer 12 intermediate barrier layer
13 Heat-sealable layer 14 middle layer 15 lower surface layer
20 coating a barrier layer
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; the technical features designed in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be noted that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently has certain errors. This error is a corollary to the standard deviation found in its corresponding measurement method.
Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
The individual components of the present invention will be explained in more detail below.
The embodiment of the invention provides a high-barrier heat-sealable degradable film, which comprises a substrate layer 10 and a coating barrier layer 20 positioned on the upper surface of the substrate layer 10;
the coating barrier layer 20 includes polyvinyl alcohol emulsion, graphene, adhesive resin, a curing agent, a coupling agent, and a solvent.
Specifically, the coating barrier layer 20 has a better barrier property due to the synergistic effect of the inorganic barrier agent and the organic barrier agent. The graphene lamellar structure is uniformly dispersed in the film through the coating liquid, so that the path of oxygen permeation is prolonged, the gas barrier property is improved, the barrier property is not influenced by temperature and humidity, meanwhile, the polyvinyl alcohol has good barrier property, the addition of the component can fill the gaps between the graphene inorganic lamellar structures, a more compact film is formed, and a better barrier effect is achieved.
In some embodiments, the polyvinyl alcohol emulsion can be prepared by the following preparation method:
adding polyvinyl alcohol into a reaction kettle, setting the temperature at 75-120 ℃, stirring for 0.5-5 hours at 100-500 rpm, standing for 10-120 min, filtering, and defoaming to obtain a polyvinyl alcohol emulsion; of course, the polyvinyl alcohol emulsion can also be a conventional commercial product in the field, and will not be described in detail herein.
In some embodiments, the coating barrier layer 20 contains polyvinyl alcohol emulsion, graphene, adhesive resin, curing agent, coupling agent, and solvent in a mass ratio of (30-50): (0.1-10): (5-20): (0.1-5): (0.5-5): (10-64.3). The adhesive resin is prepared from butyl methacrylate, ethylene glycol dimethacrylate and polyurethane resin according to the mass part of 2: 1: 1 are mixed. The curing agent is diethyl malonic acid blocked isocyanate. The coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the solvent is formed by mixing water and isopropanol according to the mass ratio of 3: 1.
In order to further improve the barrier performance and other performances of the film material, the substrate layer 10 at least comprises a three-layer structure, and an upper layer 11, a middle barrier layer 12 and a heat sealing layer 13 are sequentially arranged from top to bottom;
wherein the upper surface layer 11 comprises, by mass, 1-5 parts of functional master batches and 95-99 parts of polylactic resin. The functional master batch comprises 0.5-5 parts of lubricant, 1-10 parts of opening agent, 0.5-5 parts of antioxidant and 80-98 parts of polylactic resin, and the preparation method comprises the steps of obtaining preparation raw materials according to the proportion, and performing melt extrusion, bracing, cooling, grain extraction and drying at the temperature of 120-210 ℃ by using a double-screw extruder to obtain the functional master batch; the lubricant is preferably one or two of erucamide and oleamide; the opening agent is preferably silicon dioxide; the antioxidant is preferably prepared from antioxidant 1010 and antioxidant 168 according to the ratio of 2: 1, and mixing to obtain the product.
The middle barrier layer 12 comprises, by mass, 0.1-5 parts of a layered nano inorganic material, 0.1-8 parts of a coupling agent, 0.1-5 parts of a super dispersant, and 82-99.7 parts of polylactic resin. The layered nano inorganic material is preferably at least one of montmorillonite, layered silicate, mica powder and kaolin; the coupling agent is preferably, but not limited to, gamma- (2, 3-glycidoxy) propyltrimethoxysilane; the hyperdispersant is preferably, but not limited to, DP 310.
In view of the above, a preferred embodiment of the present invention provides a method for preparing a modified polylactic acid resin, comprising the steps of:
step 1: dissolving a layered nano inorganic material in deionized water, wherein the mass ratio of water to the layered nano inorganic material is 1: 10-1: 50, placing the mixed liquid container on a shaking table, shaking until the layered nano inorganic materials are uniformly dispersed, then centrifuging at the speed of 200-800 rpm for 5-20 min, taking the upper-layer mixed liquid, removing large-particle-size particles at the bottom of a centrifuge tube, centrifuging the collected upper-layer mixed liquid at the speed of 3000-6000 rpm, removing supernatant, scraping the layered nano inorganic materials at the bottom of the centrifuge tube, drying at the temperature of 50-80 ℃, and then grinding and sieving;
step 2: the method comprises the following steps of (1) mixing the layered nano inorganic material obtained in Step1 with deionized water in a mass ratio of 1: 5, adding the mixture into a reaction kettle, adding an organic treating agent (the organic treating agent is preferably dioctadecylbenzylammonium, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and methacrylic acid which are mixed according to the mass part ratio of 1: 1: 1), adding the organic treating agent, better treating the layered nano inorganic material, increasing the polarity and better ensuring the effect, wherein the added mass part of the organic treating agent is 50-200% of the total mass of the layered nano inorganic material, stirring the mixture in a water bath at the temperature of 60-90 ℃ for reaction for 1-3 h, washing the mixture with deionized water after centrifugation until no Br exists in the washed solution-(with AgNO)3Detection). Then drying at 50-70 ℃, grinding and sieving with a 500-mesh sieve, and finally activating at 100-120 ℃ for 1-5 h to obtain an organic treatment layered nano inorganic material;
step 3: placing an organically treated layered nano inorganic material prepared from a coupling agent gamma-methacryloxypropyltrimethoxysilane, a super dispersant and Step2 into a stirrer, stirring at the speed of 300-500 rpm for 3-6 minutes, adding polylactic resin, and performing high-speed mixing for 10-25 min in a high-speed stirring mode to obtain a mixture;
step 4: and adding the mixture obtained in Step3 into a double-screw extruder, and performing melt extrusion, bracing, cooling, grain extraction and drying at the temperature of 120-210 ℃ to obtain the modified polylactic resin.
The layered nano inorganic material in the modified polylactic resin is stripped under the action of the shearing force of the screw, the layered structure is dispersed in the polymer film to form a plurality of parallel and stacked two-dimensional sheets, and small molecular substances such as oxygen and the like cannot directly permeate the film and can only permeate through gaps between layers. Therefore, the addition of the layered nano inorganic material can block the permeation of oxygen and other small molecular substances, and has a tortuous labyrinth effect, which is equivalent to prolonging the permeation path of oxygen and other small molecular substances, and finally reduces the permeation amount of oxygen and other small molecular substances;
furthermore, the barrier properties between the coating barrier layer and the middle barrier layer form complementary advantages and strong combination to form barrier double insurance, and the barrier layer has better barrier property than a single barrier layer, thereby greatly improving the barrier property of the film.
The heat sealing layer 13 comprises, by mass, 1-10 parts of a compatilizer, 1-5 parts of a functional master batch, 25-80 parts of polyethylene terephthalate-1, 4-cyclohexanedimethanol ester and 5-73 parts of polylactic resin. The compatilizer is preferably at least one of ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, ethylene-acrylate-maleic anhydride copolymer, ethylene-vinyl acetate copolymer, maleic anhydride grafted ethylene-octene copolymer, ethylene-acrylic acid copolymer and glycidyl methacrylate grafted ethylene-octene copolymer; the functional master batch comprises 0.5-5 parts of lubricant, 1-10 parts of opening agent, 0.5-5 parts of antioxidant and 80-98 parts of polylactic resin, and the preparation method comprises the steps of obtaining preparation raw materials according to the proportion, and performing melt extrusion, bracing, cooling, grain extraction and drying at the temperature of 120-210 ℃ by using a double-screw extruder to obtain the functional master batch; the lubricant is preferably one or two of erucamide and oleamide; the opening agent is preferably silicon dioxide; the antioxidant is preferably prepared from antioxidant 1010 and antioxidant 168 according to the ratio of 2: 1, and mixing to obtain the product.
Further, in order to make the function of the high-barrier heat-sealable degradable film more excellent and practical, the total thickness of the high-barrier heat-sealable degradable film is 10-80 μm; wherein the thickness of the coating barrier layer 20 is 1 to 4 μm; the thickness of the upper surface layer 11 and the heat sealing layer 13 is 1-3 μm; the thickness of the intermediate barrier layer 12 is 7 to 70 μm.
An embodiment of the invention provides a preparation method of a high-barrier heat-sealable degradable film, which comprises the following steps:
obtaining a substrate layer;
disposing a coating barrier layer on an upper surface of the substrate layer; the coating barrier layer comprises polyvinyl alcohol emulsion, graphene, bonding resin, a curing agent, a coupling agent and a solvent.
Specifically, an embodiment of the invention provides a preparation method of a high-barrier heat-sealable degradable film, which comprises the following steps:
(1) preparing a base material layer:
step 1: drying all raw materials of the substrate layer (including the raw material of the upper surface layer, the raw material of the intermediate barrier layer and the raw material of the heat-sealing layer), and controlling the moisture content of the raw materials to be less than 100 ppm;
step 2: mixing the raw materials of the upper surface layer, the middle barrier layer and the heat sealing layer according to a formula ratio, melting, plasticizing and extruding the raw materials at the temperature of 170-210 ℃ through respective extruders, and flowing out through a T-shaped die head;
step 3: attaching the melt to a cold drum by using a low-pressure air knife to form a thick sheet, wherein the thickness of the thick sheet is 100-350 mu m, and the temperature of the cold drum is 10-50 ℃;
step 4: immersing the thick sheet into a water tank at the temperature of 20-80 ℃ for pretreatment;
step 5: heating the thick sheet, and then performing synchronous biaxial stretching on the polylactic acid film by adopting Brookner magnetic suspension synchronous biaxial stretching equipment, wherein the stretching temperature is 90-180 ℃, and the stretching ratio is 3.5 x 3.5-5.5 x 5.5;
step 6: carrying out heat setting treatment on the stretched film, wherein the setting temperature is 140-190 ℃, the setting time is 5-40 s, then carrying out cooling and corona post-treatment on the film, and the corona treatment power is 10-15 Wmin/m2And rolling;
step 7: and cutting the rolled two-way stretched polylactic acid film according to the requirement to finally obtain the substrate layer.
(2) Preparation of coating liquid:
step 1: adding a coupling agent into graphene, and stirring at a high speed of 800-1200 rpm for 5-20 min to obtain a first mixture;
step 2: adding a solvent into a reaction kettle, slowly adding a polyvinyl alcohol emulsion at the rotating speed of 100-300 rpm, and continuously stirring for 5-10 min until the mixture is completely and uniformly dispersed to obtain a second mixture;
step 3: gradually adding the first mixture into the second mixture, and stirring at the rotating speed of 300-800 rpm for 10-40 min to obtain a third mixture;
step 4: adding bonding resin into the third mixture at the rotating speed of 100-400 rpm, and continuously stirring for 5-20 min;
step 5: and finally, adding a curing agent, and stirring at the rotating speed of 200-600 rpm for 10-60 min to obtain the coating liquid.
(3) Preparation of a coating barrier layer:
and placing the substrate layer film on a unreeling shaft of a coating machine, pouring the coating liquid into a glue tank, adjusting parameters of the coating machine to coat the surface of the upper surface layer of the substrate layer, sending the coated film into a drying oven at 70-120 ℃ for drying, rolling and placing the film into a curing chamber at 40-65 ℃ for curing for 24-72 hours to obtain the high-barrier heat-sealable degradable film.
For a better understanding of the invention, the invention is described in detail below with reference to specific examples and to the scale, without restricting the invention in any way.
Example 1
The embodiment provides a high-barrier heat-seal degradable film, please refer to fig. 1, the high-barrier heat-seal degradable film comprises a coating barrier layer 20 and a substrate layer 10, the substrate layer 10 is composed of three layers, an upper layer 11, a middle barrier layer 12 and a heat seal layer 13 are sequentially arranged from top to bottom, and the coating barrier layer 20 is located on the upper surface of the substrate layer 10.
The upper surface layer comprises 3 parts of functional master batch and 97 parts of polylactic resin in parts by mass;
wherein the functional master batch comprises 4 parts of lubricant, 8 parts of opening agent, 1 part of antioxidant and 87 parts of polylactic resin; the lubricant is erucamide; the opening agent is silicon dioxide; the antioxidant is prepared by mixing an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 2: 1, mixing; the functional master batch is obtained by melt extrusion, bracing, cooling, grain extraction and drying at the temperature of 200 ℃ through a double-screw extruder. .
The middle barrier layer is 100 parts of modified polylactic resin by mass;
wherein the modified polylactic resin contains 3 parts of layered nano inorganic material, 3 parts of coupling agent, 1 part of super dispersant and 93 parts of polylactic resin; the layered nano inorganic material is montmorillonite; the coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the hyperdispersant is DP 310. The modified polylactic resin is obtained by blending and modifying double screws, and the preparation method comprises the following steps:
step 1: dissolving a layered nano inorganic material in deionized water, wherein the mass ratio of water to the layered nano inorganic material is 1: 20, placing the mixed liquid container on a shaking table, shaking until the layered nano inorganic materials are uniformly dispersed, then centrifuging at the speed of 500rpm for 10min, taking the upper-layer mixed liquid, removing large-particle-size particles at the bottom of the centrifuge tube, centrifuging the collected upper-layer mixed liquid at the speed of 5000rpm, removing supernatant, scraping the layered nano inorganic materials at the bottom of the centrifuge tube, drying at 70 ℃, and then grinding and sieving;
step 2: according to the mass part ratio of the layered nano inorganic material to the deionized water of 1: 5, adding the mixture into a reaction kettle, simultaneously adding an organic treating agent (the organic agent is dioctadecylmethylbenzylammonium, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and methacrylic acid which are mixed according to the mass part ratio of 1: 1: 1), wherein the added mass part of the organic treating agent is 60 percent of that of the layered nano inorganic material, stirring the mixture in a water bath at 70 ℃ for reaction for 2 hours, centrifuging the mixture, and washing the mixture by deionized water until no Br is generated in the washed solution-(with AgNO)3Detection). Then drying at 60 ℃, grinding and sieving with a 500-mesh sieve, and finally activating at 110 ℃ for 3h to obtain the organically treated layered nano inorganic material;
step 3: putting a coupling agent gamma-methacryloxypropyltrimethoxysilane, a super dispersant and an organically treated layered nano inorganic material into a stirrer, stirring at the speed of 400rpm for 5 minutes, then adding polylactic resin, and high-speed mixing for 15 minutes in a high-speed stirring mode to obtain a mixture;
step 4: adding the mixture into a double-screw extruder, and performing melt extrusion, bracing, cooling, grain extraction and drying at the temperature of 200 ℃ to obtain the modified polylactic resin.
The heat sealing layer comprises, by mass, 5 parts of a compatilizer, 3 parts of a functional master batch, 50 parts of polyethylene terephthalate-1, 4-cyclohexanedimethanol ester and 42 parts of polylactic resin;
wherein the compatilizer is glycidyl methacrylate grafted ethylene-octene copolymer; the functional master batch comprises 4 parts of lubricant, 8 parts of opening agent, 1 part of antioxidant and 87 parts of polylactic resin; the lubricant is erucamide; the opening agent is silicon dioxide; the antioxidant is prepared by mixing an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 2: 1, mixing; the functional master batch is obtained by melt extrusion, bracing, cooling, grain extraction and drying at the temperature of 200 ℃ through a double-screw extruder.
The coating barrier layer comprises, by mass, 40 parts of polyvinyl alcohol emulsion, 1 part of graphene, 10 parts of bonding resin, 2 parts of curing agent, 2 parts of coupling agent and 45 parts of solvent;
wherein the adhesive resin is prepared from butyl methacrylate, ethylene glycol dimethacrylate and polyurethane resin according to the mass part of 2: 1: 1, mixing; the curing agent is diethyl malonic acid blocked isocyanate; the coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the solvent is water and isopropanol according to a ratio of 3:1, and mixing the components in a mass ratio of 1.
The thickness of the high-barrier heat-sealable degradable film is 30 mu m; wherein the thickness of the coating barrier layer is 2 μm; the thickness of the upper surface layer and the heat sealing layer is 1.5 mu m; the thickness of the intermediate barrier layer was 25 μm.
Further, the preparation method of the high-barrier heat-sealable degradable film comprises the following steps:
preparing a base material layer:
step 1: drying all raw materials, and controlling the moisture content of the raw materials to be below 100 ppm;
step 2: mixing the raw materials of the upper surface layer, the middle barrier layer and the heat sealing layer according to the formula proportion respectively, then performing melt plasticizing extrusion at the temperature of 195 ℃ through respective extruders, and allowing the mixture to flow out through a T-shaped die head;
step 3: attaching the melt to a cold drum by using a low-pressure air knife to form a thick sheet, wherein the thickness of the thick sheet is 230 mu m, and the temperature of the cold drum is 30 ℃;
step 4: immersing the thick sheet into a water tank at 50 ℃ for pretreatment;
step 5: heating the thick sheet, and then performing synchronous biaxial stretching on the polylactic acid film by adopting Brookner magnetic suspension synchronous biaxial stretching equipment, wherein the stretching temperature is 120 ℃, and the stretching ratio is 4.5 x 4.5;
step 6: heat setting the stretched film at 170 deg.c for 12 sec, cooling and corona post-treatment at corona power of 12Wmin/m2And rolling;
step 7: and slitting the rolled biaxially-oriented polylactic acid film according to the requirement to finally obtain the high-barrier degradable biaxially-oriented film, wherein the thickness of the film is 28 microns.
Preparation of coating liquid:
step 1: adding a coupling agent into graphene, and stirring at a high speed for 10min under the condition of 1000rpm to obtain a first mixture;
step 2: adding a solvent into a reaction kettle, slowly adding a polyvinyl alcohol emulsion at the rotating speed of 200rpm, and continuously stirring for 6min until the mixture is completely and uniformly dispersed to obtain a second mixture;
step 3: gradually adding the first mixture into the second mixture, and stirring at 500rpm for 20min to obtain a third mixture;
step 4: adding bonding resin into the third mixture at the rotating speed of 300rpm, and continuously stirring for 10 min;
step 5: and finally, adding a curing agent, and stirring at the rotating speed of 400rpm for 30min to obtain the coating liquid.
Preparation of a coating barrier layer:
and placing the substrate layer film on a unreeling shaft of a coating machine, pouring the coating liquid into a glue tank, adjusting parameters of the coating machine to coat the surface of the upper surface layer of the substrate layer, sending the coated film into a drying oven at 110 ℃ to be dried, rolling and placing the film into a curing chamber at 50 ℃ to be cured for 48 hours, and obtaining the high-barrier heat-sealing degradable film.
Example 2
The embodiment provides a high-barrier heat-seal degradable film, please refer to fig. 1, the high-barrier heat-seal degradable film comprises a coating barrier layer 20 and a substrate layer 10, the substrate layer 10 is composed of three layers, an upper layer 11, a middle barrier layer 12 and a heat-seal layer 13 are sequentially arranged from top to bottom, and the coating barrier layer 20 is located on the upper surface of the substrate layer 10.
The upper surface layer comprises 4 parts of functional master batches and 96 parts of polylactic resin in parts by mass;
wherein the functional master batch comprises 4 parts of lubricant, 8 parts of opening agent, 1 part of antioxidant and 87 parts of polylactic resin; the lubricant is erucamide; the opening agent is silicon dioxide; the antioxidant is prepared by mixing an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 2: 1, mixing; the functional master batch is obtained by melt extrusion, bracing, cooling, grain extraction and drying at the temperature of 200 ℃ through a double-screw extruder. .
The middle barrier layer is 100 parts of modified polylactic resin by mass;
wherein the modified polylactic resin contains 4 parts of layered nano inorganic material, 3.5 parts of coupling agent, 1.5 parts of super dispersant and 91 parts of polylactic resin; the layered nano inorganic material is prepared from montmorillonite and mica powder in parts by mass as follows: 1, mixing; the coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the hyperdispersant is DP 310. The modified polylactic resin is obtained by blending and modifying double screws, and the preparation method comprises the following steps:
step 1: dissolving a layered nano inorganic material in deionized water, wherein the mass ratio of water to the layered nano inorganic material is 1: 30, placing the mixed liquid container on a shaking table, shaking until the layered nano inorganic materials are uniformly dispersed, then centrifuging at the speed of 600rpm for 15min, taking the upper-layer mixed liquid, removing large-particle-size particles at the bottom of a centrifuge tube, centrifuging the collected upper-layer mixed liquid at the speed of 5500rpm, removing supernatant, scraping the layered nano inorganic materials at the bottom of the centrifuge tube, drying at the temperature of 75 ℃, and then grinding and sieving;
step 2: according to the mass part ratio of the layered nano inorganic material to the deionized water of 1: 5, adding the mixture into a reaction kettle, simultaneously adding an organic treating agent (the organic agent is dioctadecylmethylbenzylammonium, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and methacrylic acid which are mixed according to the mass part ratio of 1: 1: 1), wherein the added mass part of the organic treating agent is 80 percent of that of the layered nano inorganic material, stirring the mixture in a water bath at the temperature of 80 ℃ for reaction for 2.5 hours, centrifuging the mixture, and washing the mixture by using deionized water until no Br exists in the washed solution-(with AgNO)3Detection). Then drying at 65 ℃, grinding and sieving with a 500-mesh sieve, and finally activating at 115 ℃ for 4h to obtain an organic processing layered nano inorganic material;
step 3: putting a coupling agent gamma-methacryloxypropyltrimethoxysilane, a super dispersant and an organically treated layered nano inorganic material into a stirrer, stirring for 4 minutes at the speed of 450rpm, then adding polylactic resin, and highly mixing for 20 minutes in a high-speed stirring mode to obtain a mixture;
step 4: adding the mixture into a double-screw extruder, and performing melt extrusion, bracing, cooling, grain extraction and drying at the temperature of 195 ℃ to obtain the modified polylactic resin.
The heat sealing layer comprises 8 parts of compatilizer, 4 parts of functional master batch, 60 parts of polyethylene glycol terephthalate-1, 4-cyclohexanedimethanol ester and 28 parts of polylactic resin in parts by mass;
the compatilizer is an ethylene-methyl acrylate-glycidyl methacrylate random terpolymer and an ethylene-acrylate-maleic anhydride copolymer, and the weight ratio of the ethylene-methyl acrylate-glycidyl methacrylate random terpolymer to the ethylene-acrylate-maleic anhydride copolymer is 1: 1, mixing; the functional master batch comprises 4 parts of lubricant, 8 parts of opening agent, 1 part of antioxidant and 87 parts of polylactic resin; the lubricant is erucamide; the opening agent is silicon dioxide; the antioxidant is prepared by mixing an antioxidant 1010 and an antioxidant 168 according to the weight ratio of 2: 1, mixing; the functional master batch is obtained by melt extrusion, bracing, cooling, grain extraction and drying at the temperature of 200 ℃ through a double-screw extruder.
The coating barrier layer comprises, by mass, 45 parts of polyvinyl alcohol emulsion, 2 parts of graphene, 15 parts of bonding resin, 2.5 parts of curing agent, 3 parts of coupling agent and 32.5 parts of solvent;
wherein the adhesive resin is prepared from butyl methacrylate, ethylene glycol dimethacrylate and polyurethane resin according to the mass part of 2: 1: 1, mixing; the curing agent is diethyl malonic acid blocked isocyanate; the coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the solvent is water and isopropanol according to a ratio of 3:1, and mixing the components in a mass ratio of 1.
The thickness of the high-barrier heat-sealable degradable film is 30 mu m; wherein the thickness of the coating barrier layer is 2.5 μm; the thickness of the upper surface layer and the heat sealing layer is 2 μm; the thickness of the intermediate barrier layer was 23.5 μm.
Further, the preparation method of the high-barrier heat-sealable degradable film comprises the following steps:
preparing a base material layer:
step 1: drying all raw materials, and controlling the moisture content of the raw materials to be below 100 ppm;
step 2: mixing the raw materials of the upper surface layer, the middle barrier layer and the heat sealing layer according to the formula proportion respectively, then performing melt plasticizing extrusion at the temperature of 200 ℃ through respective extruders, and allowing the mixture to flow out through a T-shaped die head;
step 3: attaching the melt to a cold drum by using a low-pressure air knife to form a thick sheet, wherein the thickness of the thick sheet is 250 mu m, and the temperature of the cold drum is 25 ℃;
step 4: immersing the thick sheet into a water tank at 55 ℃ for pretreatment;
step 5: heating the thick sheet, and then performing synchronous biaxial stretching on the polylactic acid film by adopting Brookner magnetic suspension synchronous biaxial stretching equipment, wherein the stretching temperature is 125 ℃, and the stretching ratio is 4.8 x 4.8;
step 6: the stretched film is subjected to heat setting treatment, wherein the setting temperature is 168 ℃, the setting time is 15s, then the film is subjected to cooling and corona post-treatment, and the corona treatment power is 11Wmin/m2And rolling;
step 7: and slitting the rolled biaxially-oriented polylactic acid film according to the requirement to finally obtain the high-barrier degradable biaxially-oriented film, wherein the thickness of the film is 30 mu m.
Preparation of coating liquid:
step 1: adding a coupling agent into graphene, and stirring at a high speed for 15min under the condition of 1100rpm to obtain a first mixture;
step 2: adding a solvent into a reaction kettle, slowly adding a polyvinyl alcohol emulsion at the rotating speed of 250rpm, and continuously stirring for 8min until the mixture is completely and uniformly dispersed to obtain a second mixture;
step 3: gradually adding the first mixture into the second mixture, and stirring at 600rpm for 30min to obtain a third mixture;
step 4: adding bonding resin into the third mixture at the rotating speed of 350rpm, and continuously stirring for 15 min;
step 5: and finally, adding a curing agent, and stirring at the rotating speed of 500rpm for 40min to obtain the coating liquid.
Preparation of a coating barrier layer:
and placing the substrate layer film on a unreeling shaft of a coating machine, pouring the coating liquid into a glue tank, adjusting parameters of the coating machine to coat on the surface of the upper surface layer of the substrate layer, sending the film into a 115-DEG C drying oven to be dried after coating, then rolling and placing the film into a 45-DEG C curing chamber to be cured for 72 hours, and obtaining the high-barrier heat-sealable degradable film.
Comparative example 1
In this embodiment, referring to fig. 2, the film is composed of three layers, which are an upper layer 11, a middle layer 14 and a lower layer 15 from top to bottom. The upper surface layer comprises 3 parts of functional master batches and 97 parts of polylactic resin in parts by mass; the middle layer is 100 parts of polylactic resin; the lower surface layer comprises 3 parts of functional master batch and 97 parts of polylactic resin.
The preparation method of the functional master batch is the same as that of the embodiment 1, and the preparation method of the film comprises the following steps:
step 1: drying all raw materials, and controlling the moisture content of the raw materials to be below 100 ppm;
step 2: mixing the raw materials of the upper surface layer, the middle layer and the lower surface layer according to the formula proportion, melting, plasticizing and extruding at 195 ℃ through respective extruders, and flowing out through a T-shaped die head;
step 3: attaching the melt to a cold drum by using a low-pressure air knife to form a thick sheet, wherein the thickness of the thick sheet is 230 mu m, and the temperature of the cold drum is 30 ℃;
step 4: immersing the thick sheet into a water tank at 50 ℃ for pretreatment;
step 5: heating the thick sheet, and then performing synchronous biaxial stretching on the polylactic acid film by adopting Brookner magnetic suspension synchronous biaxial stretching equipment, wherein the stretching temperature is 120 ℃, and the stretching ratio is 4.5 x 4.5;
step 6: heat setting the stretched film at 170 deg.c for 12 sec, cooling and corona post-treatment at corona power of 12Wmin/m2And rolling;
step 7: and slitting the rolled biaxially-oriented polylactic acid film according to the requirement to finally obtain the high-barrier degradable biaxially-oriented film, wherein the thickness of the film is 30 mu m.
Comparative example 2
In this embodiment, referring to fig. 3, the film is composed of three layers, which are, from top to bottom, an upper layer 11, a middle barrier layer 12 and a heat-sealing layer 13. The upper surface layer comprises 3 parts of functional master batches and 97 parts of polylactic resin in parts by mass; the middle barrier layer is 100 parts of modified polylactic resin; the heat sealing layer comprises 5 parts of compatilizer, 3 parts of functional master batch, 50 parts of polyethylene terephthalate-1, 4-cyclohexane dimethanol ester and 42 parts of polylactic resin.
In comparative example 2, the materials and preparation method were the same as those in example 1 except that the coating barrier layer was not provided.
Comparative example 3
The present embodiment provides a film, please refer to fig. 4, the film includes a coating barrier layer 20 and a substrate layer 10, the substrate layer 10 is composed of a three-layer structure, which includes an upper layer 11, a middle layer 14 and a heat-sealing layer 13 from top to bottom, and the coating barrier layer 20 is located on the upper surface of the substrate layer 10. The upper surface layer comprises 3 parts of functional master batches and 97 parts of polylactic resin in parts by mass; the middle barrier layer is 100 parts of polylactic resin; the heat sealing layer comprises 5 parts of compatilizer, 3 parts of functional master batch, 50 parts of polyethylene terephthalate-1, 4-cyclohexane dimethanol ester and 42 parts of polylactic resin.
The coating barrier layer comprises, by mass, 40 parts of polyvinyl alcohol emulsion, 1 part of graphene, 10 parts of bonding resin, 2 parts of curing agent, 2 parts of coupling agent and 45 parts of solvent;
in comparative example 3, the raw materials and preparation method were the same as those of example 1 except that the intermediate barrier layer was 100 parts of polylactic acid resin.
Comparative example 4
In this embodiment, referring to fig. 5, the film is composed of three layers, which are, from top to bottom, an upper layer 11, a middle layer 14 and a heat sealing layer 13. The upper surface layer comprises 3 parts of functional master batches and 97 parts of polylactic resin in parts by mass; the middle layer is 100 parts of polylactic resin; the heat sealing layer comprises 5 parts of compatilizer, 3 parts of functional master batch, 50 parts of polyethylene terephthalate-1, 4-cyclohexane dimethanol ester and 42 parts of polylactic resin.
In comparative example 4, 100 parts of polylactic acid resin was used for the intermediate barrier layer, except that the coating barrier layer was not provided, and the raw materials and preparation methods of the other materials were the same as those in example 1.
Comparative example 5
The present embodiment provides a film, please refer to fig. 1, the film includes a coating barrier layer 20 and a substrate layer 10, the substrate layer 10 is composed of a three-layer structure, which includes an upper layer 11, a middle barrier layer 12 and a heat-sealing layer 13 from top to bottom, and the coating barrier layer 20 is located on the upper surface of the substrate layer 10. The upper surface layer comprises 3 parts of functional master batches and 97 parts of polylactic resin in parts by mass; the middle barrier layer is 100 parts of modified polylactic resin; the heat sealing layer comprises 5 parts of compatilizer, 3 parts of functional master batch, 50 parts of polyethylene terephthalate-1, 4-cyclohexane dimethanol ester and 42 parts of polylactic resin.
The coating barrier layer comprises, by mass, 40 parts of polyvinyl alcohol emulsion, 10 parts of adhesive resin, 2 parts of curing agent, 2 parts of coupling agent and 45 parts of solvent;
the intermediate barrier layer of comparative example 5 did not contain graphene, and the remaining materials and preparation methods were the same as those of example 1.
Comparative example 6
The present embodiment provides a film, please refer to fig. 6, the film includes a coating barrier layer 20 and a substrate layer 10, the substrate layer 10 is composed of three layers, which are an upper layer 11, a middle barrier layer 12 and a lower layer 15 from top to bottom, and the coating barrier layer 20 is located on the upper surface of the substrate layer 10. The upper surface layer comprises 3 parts of functional master batches and 97 parts of polylactic resin in parts by mass; the middle barrier layer is 100 parts of modified polylactic resin; the lower surface layer comprises 3 parts of functional master batch and 97 parts of polylactic resin.
The coating barrier layer comprises, by mass, 40 parts of polyvinyl alcohol emulsion, 10 parts of adhesive resin, 2 parts of curing agent, 2 parts of coupling agent and 45 parts of solvent;
the substrate layer of comparative example 6 was not provided with a heat-seal layer, but was changed to a common polylactic acid resin layer, and the remaining material materials and the preparation method were the same as those of example 1.
Comparative example 7
The present embodiment provides a film, please refer to fig. 1, the film includes a coating barrier layer 20 and a substrate layer 10, the substrate layer 10 is composed of a three-layer structure, which includes an upper layer 11, a middle barrier layer 12 and a heat-sealing layer 13 from top to bottom, and the coating barrier layer 20 is located on the upper surface of the substrate layer 10. The upper surface layer comprises 3 parts of functional master batches and 97 parts of polylactic resin in parts by mass; the middle barrier layer is 100 parts of modified polylactic resin; the heat sealing layer comprises 5 parts of compatilizer, 3 parts of functional master batch, 50 parts of polyethylene terephthalate-1, 4-cyclohexane dimethanol ester and 42 parts of polylactic resin.
The coating barrier layer comprises 1 part of graphene, 10 parts of bonding resin, 2 parts of curing agent, 2 parts of coupling agent and 85 parts of solvent in parts by mass;
the coated barrier layer of comparative example 7 did not contain the polyvinyl alcohol emulsion, and the remaining materials and preparation methods were the same as those of example 1.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
In addition, the raw materials used may be those commercially available or prepared by methods conventional in the art, unless otherwise specified.
The examples and comparative examples were tested for various properties according to the following test criteria:
(1) testing of Heat seal Properties: the test is carried out according to the standard requirements of QB/T2358, Plastic film packaging bag heat seal strength test method.
(2) Oxygen permeability performance test: the Test was carried out according to the ASTM D3985 Standard requirement of Standard Test Method for Oxygen Gas Transmission Rate Through Plastic Film and Sheeting Using a colorimetric Sensor.
(3) In the table, symbol ".", symbol ". cndot" indicates excellent, symbol ". o" indicates excellent, symbol "□" indicates good, symbol "Δ" indicates poor, symbol "x" indicates very poor, and symbol "-" indicates no test or no test formula, no correlation data.
The relevant performance of the above examples and comparative examples was tested, and the specific result data is shown in the following table:
TABLE 1
As can be seen from the table, compared with the degradable film produced by the traditional method, the high-barrier heat-sealable degradable film prepared by the invention has better barrier property and heat-sealing property, and can meet the requirements of the packaging markets in different fields.
Based on the above, compared with the prior art, the high-barrier heat-seal degradable film provided by the invention realizes the expected functions of the film through reasonable formula design and film layer structure design, so that the high-barrier heat-seal degradable film is widely applied to various packaging fields, has good market prospect, can be degraded under natural conditions, is nontoxic, harmless and sanitary, is a green and environment-friendly packaging material, and accords with the trend and trend of environmental protection; meanwhile, the barrier property is good, the heat sealing property is realized, the application is wide, the performance is good, the primary coating process is not needed in the processing process, the production is simpler and more convenient, the manpower, material resources and financial resources can be reduced, the processing is easy, the production process is simple, the production efficiency is high, and the industrialization is easier to realize.
In addition, it will be appreciated by those skilled in the art that, although there may be many problems with the prior art, each embodiment or aspect of the present invention may be improved only in one or several respects, without necessarily simultaneously solving all the technical problems listed in the prior art or in the background. It will be understood by those skilled in the art that nothing in a claim should be taken as a limitation on that claim.
Although terms such as substrate layer, upper layer, intermediate barrier layer, heat seal layer, intermediate layer, lower layer, coating barrier layer, etc. are used more often herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention; the terms "first," "second," and the like in the description and in the claims, and in the drawings, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A high-barrier heat-sealable degradable film is characterized in that: comprises a substrate layer (10) and a coating barrier layer (20) positioned on the upper surface of the substrate layer (10);
the coating barrier layer (20) comprises polyvinyl alcohol emulsion, graphene, adhesive resin, a curing agent, a coupling agent and a solvent.
2. The high barrier heat sealable degradable film of claim 1, wherein: the mass ratio of the polyvinyl alcohol emulsion to the graphene is (30-50): (0.1-10).
3. The high barrier heat sealable degradable film of claim 1, wherein: the adhesive resin is prepared from butyl methacrylate, ethylene glycol dimethacrylate and polyurethane resin according to the mass part of 2: 1: 1, mixing; the curing agent is diethyl malonic acid blocked isocyanate; the coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the solvent is formed by mixing water and isopropanol according to the mass ratio of 3: 1.
4. The high barrier heat sealable degradable film of claim 1, wherein: the base material layer (10) at least comprises a three-layer structure which is sequentially provided with an upper surface layer (11), a middle barrier layer (12) and a heat sealing layer (13) from top to bottom;
the intermediate barrier layer (12) comprises a modified polylactic acid resin;
the modified polylactic resin comprises, by mass, 0.1-5 parts of a layered nano inorganic material, 0.1-8 parts of a coupling agent, 0.1-5 parts of a super dispersant, and 82-99.7 parts of polylactic resin.
5. The high barrier heat sealable degradable film of claim 4, wherein: the layered nano inorganic material is at least one of montmorillonite, layered silicate, mica powder and kaolin.
6. The high barrier heat sealable degradable film of claim 4, wherein: the heat sealing layer comprises, by mass, 1-10 parts of a compatilizer, 1-5 parts of a functional master batch, 25-80 parts of polyethylene terephthalate-1, 4-cyclohexanedimethanol ester and 5-73 parts of polylactic resin.
7. The high barrier heat sealable degradable film of claim 6, wherein: the compatilizer is at least one selected from ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, ethylene-acrylate-maleic anhydride copolymer, ethylene-vinyl acetate copolymer, maleic anhydride grafted ethylene-octene copolymer, ethylene-acrylic acid copolymer and glycidyl methacrylate grafted ethylene-octene copolymer.
8. The high barrier heat sealable degradable film of claim 6, wherein: the functional master batch comprises, by mass, 0.5-5 parts of a lubricant, 1-10 parts of an opening agent, 0.5-5 parts of an antioxidant and 80-98 parts of polylactic resin.
9. The high barrier heat sealable degradable film of claim 4, wherein: the total thickness of the high-barrier heat-sealing degradable film is 10-80 mu m;
wherein the thickness of the coating barrier layer (20) is 1 to 4 μm;
the thickness of the upper surface layer (11) and the heat sealing layer (13) is 1-3 mu m;
the thickness of the intermediate barrier layer (12) is 7 to 70 μm.
10. A preparation method of a high-barrier heat-sealable degradable film comprises the following steps:
obtaining a substrate layer;
disposing a coating barrier layer on an upper surface of the substrate layer; the coating barrier layer comprises polyvinyl alcohol emulsion, graphene, bonding resin, a curing agent, a coupling agent and a solvent.
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